WO2013076249A2 - Titanoxidhaltige aluminiumoxidpartikel auf basis von im elektrischen lichtbogenofen aus kalzinierter tonerde geschmolzenem korund sowie ein verfahren zu deren herstellung - Google Patents

Titanoxidhaltige aluminiumoxidpartikel auf basis von im elektrischen lichtbogenofen aus kalzinierter tonerde geschmolzenem korund sowie ein verfahren zu deren herstellung Download PDF

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Publication number
WO2013076249A2
WO2013076249A2 PCT/EP2012/073471 EP2012073471W WO2013076249A2 WO 2013076249 A2 WO2013076249 A2 WO 2013076249A2 EP 2012073471 W EP2012073471 W EP 2012073471W WO 2013076249 A2 WO2013076249 A2 WO 2013076249A2
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Prior art keywords
weight
alumina
corundum
titanium oxide
electric arc
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PCT/EP2012/073471
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German (de)
English (en)
French (fr)
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WO2013076249A3 (de
Inventor
Sebastian Sachse
Andreas BOERGER
Alexander KRAL
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Center for Abrasives and Refractories Research and Development CARRD GmbH
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Center for Abrasives and Refractories Research and Development CARRD GmbH
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Application filed by Center for Abrasives and Refractories Research and Development CARRD GmbH filed Critical Center for Abrasives and Refractories Research and Development CARRD GmbH
Priority to US14/360,170 priority Critical patent/US9163128B2/en
Priority to BR112014012106-0A priority patent/BR112014012106B1/pt
Priority to RU2014125555/05A priority patent/RU2582399C2/ru
Priority to CN201280057585.XA priority patent/CN103958413B/zh
Priority to KR1020147017004A priority patent/KR101577924B1/ko
Priority to EP12805951.6A priority patent/EP2782871B1/de
Priority to JP2014542853A priority patent/JP6034395B2/ja
Publication of WO2013076249A2 publication Critical patent/WO2013076249A2/de
Publication of WO2013076249A3 publication Critical patent/WO2013076249A3/de
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/38—Preparation of aluminium oxide by thermal reduction of aluminous minerals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
    • B02C23/08—Separating or sorting of material, associated with crushing or disintegrating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/021—After-treatment of oxides or hydroxides
    • C01F7/027—Treatment involving fusion or vaporisation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5296—Constituents or additives characterised by their shapes with a defined aspect ratio, e.g. indicating sphericity
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)

Definitions

  • the present invention relates to titanium oxide-containing aluminum oxide particles based on alumina melted in the electric arc furnace made of calcined alumina and having the features of the preamble of claim 1 and a process for the production of said alumina particles ,
  • Molten corundum is used as an abrasive and refractory because of its high hardness and high melting point.
  • the production takes place by melting the raw materials in the electric arc furnace.
  • bauxite corundums which are obtained from bauxite as raw material with the aid of a reducing melt in the electric arc furnace
  • alumina corundums which are produced chemically by alkaline digestion of bauxite. used clay as raw materials.
  • the naturally occurring bauxites essentially contain iron oxide, titanium oxide and silicon oxide as impurities, which are partially removed by the reducing melt in the electric arc furnace.
  • the known in the abrasive and refractory industry normal corundum with a TiO 2 content of about 3 6ew .-% and the semi-precious corundum with a TiO 2 content of approx.
  • the titanium oxide content affects the physical properties of the products. This is how the titanium oxide-containing materials are distinguished
  • Bauxite corundum characterized by a high toughness by a Subsequent temperature treatment can be increased even further.
  • the analysis of the titanium oxide content is an important method for quality control during the melt.
  • the carbon reduces some of the TiO 2 to Ti 2 O 3> which is to some extent soluble in alumina.
  • a characteristic steel-blue color is formed, which is due to the formation of
  • Ti 3+ / Ti 4+ phases The formation of the blue color, which is regarded as an indicator of the toughness of the aluminum oxide particles, depends strongly on the proportion of titanium oxide dissolved in solid form (Ti 2 O 3 ).
  • the second large group of fused corundum are the so-called noble corundum, which are produced in the electric arc furnace based on calcined clay.
  • noble corundum which are produced in the electric arc furnace based on calcined clay.
  • chromium oxide-doped precious corundum are also known, which are pink or dark red in color.
  • US Pat. No. 4,157,898 describes a fused alumina abrasive grain with a content of 0.42% by weight to 0.84% by weight of reduced titanium oxide.
  • DE 34 08 952 C2 describes a process for the production of corundum by reducing melting of bauxite in an electric arc, wherein bauxite is melted with the addition of metallic aluminum.
  • the semiprecious corundums used in the following for the comparative investigations were prepared according to a standard formulation according to the prior art, which was deliberately adapted to the later requirements of a production, so that returns and wastes from pre-production were used.
  • alumina-based product FR al
  • a pure alumina with Fe, Ti and Si-containing additions was used to adjust the chemical composition of a semi-precious corundum.
  • the semiprecious corundum prepared for granulation is subjected to an additional thermal aftertreatment at 1100 ° C. or 1300 ° C.
  • the corresponding post-treated products were also chemically analyzed and are listed in the table above. In the above table it can be seen that there are significant differences between the two different semi-precious corundum types FR (al) and FR (bx), in particular in the SiO 2 , Fe a O 3 , ZrO 2 and Na 2 O contents.
  • the resulting titanium oxide-containing alumina particles based on alumina are characterized in that the ratio of the sum of the weight fractions of Fe 2 O 3 , SiO a and ZrO 2 to the weight fraction of Na 2 O is ⁇ 10.
  • Alumina base carried out, which focused on the investigations of the grain shape.
  • production-grade F36 grades prepared on exactly the same crushing equipment under the same conditions, a bauxite-based standard material and an alumina-based semi-precious alumina composite were compared. Images of F36 granules were made using a light microscope and then analyzed using the image analysis software ImageJ (version 1.44 p).
  • the parameters of the image analysis software are defined as follows:
  • FIG. 2 shows side-by-side sections of enlarged light micrographs of a grain size F36 of alumina-based titanium oxide-containing alumina particles and conventional bauxite-containing aluminum oxide particles, wherein the outlines of typical grains were traced and highlighted in white in order to clarify the differences. It can be seen that the aluminum oxide particles based on alumina FR (al) have more sharp edges and are more angular than the titanium oxide-containing aluminum oxide particles based on bauxite FR (bx).
  • the present invention thus provides titanium oxide-containing aluminum oxide particles based on electric
  • the titanium oxide-containing aluminum oxide particles have an arithmetically averaged compactness of ⁇ 0.8, the measure of the compactness being the solidity (S) determined with the aid of an image analysis and defined as the ratio of the real particle area (A) to the convex particle area (B) ,
  • the titanium oxide-containing aluminum oxide particles according to the invention are moreover distinguished by the fact that the ratio of the sum of the weight fractions of Fe 2 O 3 , SiO 2 and ZrO 2 to the weight fraction of Na 2 O is ⁇ 10.
  • An advantageous embodiment of the present invention provides that the titanium-containing aluminum oxide particles have a proportion of ZrO 2 ⁇ 0.05 wt .-%.
  • the present invention also provides a process for the production of titanium oxide-containing aluminum oxide particles based on alumina melted in calcined alumina in the electric arc furnace.
  • the method comprises the
  • Particle size distributions are used as raw materials small amounts of impurities contained raw materials selected from the group consisting of calcined alumina, rutile, IImenit and iron ore, in such amounts that titanium oxide-containing alumina particles with the chemical composition Al 2 O 3 > 97.0 wt.
  • the compactness of the alumina particles thus obtained is in the arithmetic mean ⁇ 0.8, wherein the measure of the compactness, which was determined by means of an image analysis and as a ratio of the real particle area (A) to the convex
  • Particle surface (B) defined solidity (S) is.
  • the titanium oxide-containing aluminum oxide particles thus obtained are used for the production of abrasives and / or refractory materials.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
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  • Polymers & Plastics (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Thermal Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Food Science & Technology (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Nonmetallic Welding Materials (AREA)
  • Vertical, Hearth, Or Arc Furnaces (AREA)
PCT/EP2012/073471 2011-11-25 2012-11-23 Titanoxidhaltige aluminiumoxidpartikel auf basis von im elektrischen lichtbogenofen aus kalzinierter tonerde geschmolzenem korund sowie ein verfahren zu deren herstellung Ceased WO2013076249A2 (de)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US14/360,170 US9163128B2 (en) 2011-11-25 2012-11-23 Titanium oxide-containing aluminum oxide particles based on corundum melted in an electric arc furnace from calcined alumina, and a method for the production thereof
BR112014012106-0A BR112014012106B1 (pt) 2011-11-25 2012-11-23 Partículas de óxido de alumínio contendo óxido de titânio à base de coríndon fundido em um forno de arco elétrico a partir de alumina calcinada, e método para sua produção
RU2014125555/05A RU2582399C2 (ru) 2011-11-25 2012-11-23 Содержащие оксид титана частицы оксида алюминия на основе корунда, выплавленного в электродуговой печи из кальцинированного глинозема, а также способ их получения
CN201280057585.XA CN103958413B (zh) 2011-11-25 2012-11-23 基于在电弧炉中从煅烧铝氧土熔化的刚玉的含氧化钛的氧化铝颗粒及其生产方法
KR1020147017004A KR101577924B1 (ko) 2011-11-25 2012-11-23 소성 알루미나로부터 전기 아크로 내에서 용융된 코런덤을 기초로 하는 티타늄 산화물-함유 알루미늄 산화물 입자 및 그 제조 방법
EP12805951.6A EP2782871B1 (de) 2011-11-25 2012-11-23 Titanoxidhaltige aluminiumoxidpartikel auf basis von im elektrischen lichtbogenofen aus kalzinierter tonerde geschmolzenem korund sowie ein verfahren zu deren herstellung
JP2014542853A JP6034395B2 (ja) 2011-11-25 2012-11-23 焼成アルミナを電気アーク炉で溶融させたコランダムをベースとした酸化チタン含有酸化アルミニウム粒子及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011087147.0A DE102011087147B4 (de) 2011-11-25 2011-11-25 Titanoxidhaltige Aluminiumoxidpartikel auf Basis von im elektrischen Lichtbogenofen aus kalzinierter Tonerde geschmolzenem Korund sowie ein Verfahren zu deren Herstellung und ihre Verwendung
DE102011087147.0 2011-11-25

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WO2013076249A2 true WO2013076249A2 (de) 2013-05-30
WO2013076249A3 WO2013076249A3 (de) 2013-08-01

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PCT/EP2012/073471 Ceased WO2013076249A2 (de) 2011-11-25 2012-11-23 Titanoxidhaltige aluminiumoxidpartikel auf basis von im elektrischen lichtbogenofen aus kalzinierter tonerde geschmolzenem korund sowie ein verfahren zu deren herstellung

Country Status (9)

Country Link
US (1) US9163128B2 (enExample)
EP (1) EP2782871B1 (enExample)
JP (1) JP6034395B2 (enExample)
KR (1) KR101577924B1 (enExample)
CN (1) CN103958413B (enExample)
BR (1) BR112014012106B1 (enExample)
DE (1) DE102011087147B4 (enExample)
RU (1) RU2582399C2 (enExample)
WO (1) WO2013076249A2 (enExample)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013111006A1 (de) * 2013-10-04 2015-04-09 Center For Abrasives And Refractories Research & Development C.A.R.R.D. Gmbh Polykristalline poröse Al2O3-Körper auf Basis von geschmolzenem Aluminiumoxid mit erhöhter Zähigkeit, Verfahren zu ihrer Herstellung sowie ihre Verwendung
US9163128B2 (en) 2011-11-25 2015-10-20 Center For Abrasives And Refractories Research & Development C.A.R.R.D. Gmbh Titanium oxide-containing aluminum oxide particles based on corundum melted in an electric arc furnace from calcined alumina, and a method for the production thereof
RU2620800C1 (ru) * 2015-12-08 2017-05-29 федеральное государственное автономное образовательное учреждение высшего образования "Казанский (Приволжский) федеральный университет" (ФГАОУ ВО КФУ) Способ получения плавленого корунда

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CN105622074A (zh) * 2016-01-03 2016-06-01 安徽律正科技信息服务有限公司 一种用于金属精细研磨的研磨石
SI3475378T1 (sl) * 2016-06-28 2020-12-31 Showa Denko K.K., Elektrotaljena zrna aluminijevega oksida, proizvodni postopek za elektrotaljena zrna aluminijevega oksida, brusilni kamen in oplaščen abraziv
CN109092514B (zh) * 2018-07-25 2021-04-06 信阳核工业新材料有限公司 一种高流动性石英粉的制备方法
CN109181642B (zh) * 2018-10-08 2020-11-03 贵州银星新材料科技有限公司 一种半脆刚玉磨料及其制备方法
CN112592162A (zh) * 2020-12-15 2021-04-02 洛阳利尔功能材料有限公司 一种电熔白刚玉生产工艺
KR20230171168A (ko) 2022-06-13 2023-12-20 주식회사 엔디소프트 화자분할 기술이 적용된 앱을 이용한 단말기 음성 대화 방법

Citations (2)

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Publication number Priority date Publication date Assignee Title
US4157898A (en) 1976-06-01 1979-06-12 The Carborundum Company Fused aluminum oxide abrasive grain containing reduced titanium oxide
DE3408952C2 (de) 1984-03-12 1986-08-28 Richard Dipl.-Chem. 7888 Rheinfelden Sroka Verfahren zur Herstellung von Korund durch reduzierendes Schmelzen von Bauxit im elektrischen Lichtbogen

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US4111668A (en) * 1976-06-01 1978-09-05 The Carborundum Company Fused aluminum oxide abrasive grain containing reduced titanium oxide
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BR112014012106A2 (pt) 2017-08-22
WO2013076249A3 (de) 2013-08-01
US9163128B2 (en) 2015-10-20
KR20140095570A (ko) 2014-08-01
RU2014125555A (ru) 2015-12-27
DE102011087147B4 (de) 2015-02-26
EP2782871B1 (de) 2019-01-09
CN103958413A (zh) 2014-07-30
DE102011087147A1 (de) 2013-05-29
CN103958413B (zh) 2016-01-13
JP2015501777A (ja) 2015-01-19
KR101577924B1 (ko) 2015-12-15
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